Studies on dye loss mechanism of reactive dyeings

活性染料染色失色机理研究

• 批准号: 16500480
• 负责人: OKADA Yasuyo
• 金额: $ 2.37万
• 依托单位: Otsuma Women's University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16500480/
• 关键词: reactive dye; azo dye; electrophilic frontier density; PM5 method; ene reaction; reaction with singlet oxygen; [2+2] cycloaddition; azo-hydrazone tautomerism; 半経験的分子軌道法; 生成熱; セルロース上の互変異性; アゾ-ヒドラゾンの互変異性; 酸解離のアゾ-ヒドラゾン互変異性

(1)The azo-hydrazone tautomerism (AHT) was analyzed through the enthalpies of formation estimated for ten yellow reactive dyes in their hydrolyzed forms using semiempirical molecular orbital (MO) PM5 and COSMO methods according to the group additivity analysis of the AHT.(2)Photo-oxidative fading of reactive pyrazolinylazo and azobenzene dyes (seven) and of reactive azo dyes derived from J-acid and γ-acid (eleven) was examined by exposing the dyed cellulose films immersed in an aerobic aqueous Rose Bengal solution to a carbon arc. The ease with which the dye was photo-oxidized was determined as k_0, the second-order rate constant of the reaction of the dye with ^1O_2. Using the same procedure to determine the AHT, reported above, the reactivity of the tautomer of dyes toward ^1O_2 was analyzed according to frontier orbital theory. The probable reaction modes are ene and [2+2] cycloaddition towards the double bonds. The k_0-values obtained had a close correlation with the sum of Fukui's electrophilic frontier densities, f_r^<(E)>, at both atoms of the corresponding double bonds, a linear correlation between log k_0 and the sum of f_r^<(E)>, although the correlation lines for the eleven dyes differed from the correlation lines for seven pyrazolinylazo and azobenzene dyes.

（1）根据偶氮-腙互变异构体（AHT）的基团加和性分析，采用半经验分子轨道（MO）PM 5和COSMO方法，对10种黄色活性染料水解产物的生成速率进行了估算，分析了AHT的基团加和性。（2）将染料染色后的纤维素膜浸入虎红的有氧水溶液中，用碳弧照射，研究了活性吡唑啉偶氮和偶氮苯染料（7）以及J酸和γ酸衍生的活性偶氮染料（11）的光氧化褪色。染料被光氧化的难易程度用k_0表示，k_0是染料与^1O_2反应的二级速率常数。使用与上述测定AHT相同的方法，根据前线轨道理论分析了染料互变异构体对^1O_2的反应性。可能的反应模式为烯加成和向双键的[2+2]环加成。所得到的k_0值与相应双键的两个原子处的福井亲电前沿密度之和f_r^<（E）>有密切的相关性，log k_0与f_r^<（E）>之和之间有线性相关性，尽管11种染料的相关线与7种吡唑啉偶氮和偶氮苯染料的相关线不同。

项目成果

An Analysis of Azo-Hydrazone Tautomerism of Reactive Azobenzene And Pyrazolinylazo Dyes, using the Semiempirical Molecular Orbital PM5 Method,

使用半经验分子轨道 PM5 方法分析活性偶氮苯和吡唑啉基染料的偶氮腙互变异构，

• 发表时间: 2004
• 期刊: Dyes and Pigments 61(3)
• 作者: T.Hihara;Y.Okada;Z.Morita
• 通讯作者: Z.Morita

家政学事典[新版]

家政百科全书【新版】

• 发表时间: 2004
• 作者: T.Hihara;Y.Okada;Z.Morita;加藤 唯;岡田 安代(分担執筆);加藤 唯;足立 三佳;片山 倫子 他
• 通讯作者: 片山 倫子 他

家政学事典〔新版〕

家政百科全书【新版】

• 发表时间: 2004
• 作者: T.Hihara;Y.Okada;Z.Morita;加藤 唯;岡田 安代(分担執筆)
• 通讯作者: 岡田 安代(分担執筆)

An Analysis of Azo-Hydrazone Tautomerism of Reactive Azobenzene and Pyrazolinylazo Dyes,using the Semiempirical Molecular Orbital PM5 Method.

活性偶氮苯和吡唑啉基偶氮染料偶氮腙互变异构的分析，采用半经验分子轨道PM5方法。

• 发表时间: 2004
• 期刊: Dyes Pigm., 61(3)
• 作者: T.Hihara;Y.Okada;Z.Morita
• 通讯作者: Z.Morita

A semiempirical molecular orbital study of the photo-reactivity of monoazo reactive dyes derived from γ-and J-acid,

对源自 γ-和 J-酸的单偶氮活性染料的光反应性进行半经验分子轨道研究，

• 期刊: Dyes Pigm., in press.
• 作者: T.Hihara;Y.Okada;Z.Morita
• 通讯作者: Z.Morita